2-hydroxy-3-carboxyamido-benzene-azo-2-hydroxy-5, 6, 7, 8-tetrahydronaphthalene dyestuffs



United States Patent 13 Claims. (Cl. 260-202) The present inventionrelates to monoazo dyes which develop brown shades upon subsequentchromation, more particularly by the dyeing and chromation of wool andpolyamide fibers in a single neutral or slightly acid bath according tothe metachrome process.

These dyes have the general formula:

wherein X is selected from halogen atoms, and N0 groups;

Y is selected from acylamino groups, halogen-containing acylamino groupsand alkoxycarboxyamino groups.

Metachrome brown shades have generally been heretofore obtained by themetallization on fibers, of monoazodyes which are the product obtainedby coupling the diazo compounds of suitable orthoaminophenols withpara-alkyl phenol derivatives, (e.g., para-cresol, paratertiarybutylphenol, p-tert.amyl phenol, etc., and preferably tlso with othersubstitutions, such as, e.g., l-hydroxy- 2-acetamino-4-methyl benzene,1-hydroxy-2-propionyl amino-4-tertiary-butyl benzene,1-hydroxy-2-acetamino-4- tert.amyl benzene, etc).

Although a certain number of the aforementioned dyes are known from theliterature to have valuable dyeing properties, their preparationpresents considerable difiiculties due to the poor coupling tendency ofdiazotized ortho-aminophenols and the para-alkyl phenols. Moreover, whenthese phenols are substituted with alkyl chains higher than ethyl, theirsolubility in alkaline water is very slight.

When Z-hydroxy-naphthalene is used as the coupling agent, although thecoupling is facilitated, the shade of the final dye is in the area ofviolet and the dyes therefore cannot be used as brown.

It has now been surprisingly found that by using2-hydroxy-5,6,7,8-tetrahydronaphthalene as the coupling agent for dyesto be metallized on the fiber, decidely brown shades are obtained aftermetallization and, at the same time, the coupling reaction is remarkablyfacilitated. An object of the present invention is herefore to providemonoazo dyes, for wool and polyamidic fibers, which are metallizable onthe fibers during or after dyeing and have the general formula:

Patented Nov. 22, 1966 wherein X and Y have the meaning given above.

Another object of the present invention is to provide textile materialssuch as fibers, yarns and the like, which are dyed with the instantdyes.

Other objects and advantages of the present invention, will becomeapparent hereinafter.

These dyes are obtained, according to the present invention, bydiazotizing and coupling, in any conventional suitable manner, acompound of the formula:

or: NHQ

in which X and Y have the aforementioned meaning, with2-hydroxy-5,6,7,8-tetrahydronaphthalene.

The new dyes, obtained according to the present invention, are excellentfor W001 and polyamidic fibers and are suitable for a dyeing stepfollowed by a chromation treatment. Preferably, the dyeing andchromation can be carried out in a single bath, which is either neutralor slightly acid, according to the so called metachrome process.

By employing the dyes of general Formula 1, it is surprisingly simple,as is illustrated below, to obtain (after metallization) brown shadeswhich heretofore could be obtained only with certain difiiculties inpreparation.

The dyes of the present invention possess further advantages. Thus, theypossess good fastness to light even under wet conditions and also goodfastness to potting treatments, even in comparison with dyes derivedfrom alkylphenols having a higher molecular weight (e.g., p.tert.butyl,p-tertiary amyl) -and even in comparison with dyes possessing furthersubstituents such as l-hydroxy 2 acetamino-4-methylbenzene and1-hydroxy-2- acetamino-4-tert.butylbenezene. This improved fastness ofthe present dyes is probably due to the cyclic structure of the alkylsubstitution.

Among the numerous 2-arninophenol derivatives which can be usedaccording to the present invention, there can be mentioned as examples:

1-hydroxy-2-a-mino-4-nitro-6-formyl-amino-benzene,

1-hydroxy-2-amino-4-nitro-6-acetamino-benzene,

1-hydroxy-2-amino-4-nitro-6-chloro-acetamino-benzene,

1-hydroxy-2-amino-4-chloro-6-acetamino-benzene,

1-hydroxy-2-amino-4-nitro-6-propionylamino-benzene,

1 hydroxy-2-amino-4-chloro-6-propionylamino-benzene,

and

1 hydroxy 2 amino-4-nitro-6-methoxycarboxyl-aminobenzene.

The dyeing step may be carried out using any suitable conventionalprocedure. The present invention is described with reference to some ofits preferred embodiments. There are, however, obviously manymodifications and variations of the instant invention which will beevident to persons skilled in the art. For example, various phenols maybe employed as the o-aminophenol, which is coupled withZ-hydroxy-S,6,7,S-tetTahydrQnap-hthalene in order to obtain a dye to be.metallized with a brown shade. It is to be understood that these andother suitable modifications and variations are within the spirit andscope of the present invention.

The invention is illustrated but not limited by the following examplesin which all parts are by weight unless otherwise stated, and therelation between parts by weight enzene are diazotized at 5 10preferably in the pres- :nce of 0.14 part of'Dispersolo' CV(alkylphenol-e'thyl- :neoxide condensation product), 25 parts of Water,22

arts of 30% HCl and 25 parts by volume of a 4 N sodium litrite solution,with the addition of 30 parts of ice, and by ising outside cooling.

The suspension of diazo-cornpound is neutralized with odiurn carbonateand is introduced at C. into a soluion of 14.9 parts of2-hydroXy-5,6,7,8-tetrahydronaphhalene in 100 parts of Water containing4 parts of sodium iydroxide and 17 parts of sodium carbonate.

When the coupling is ended, the precipitated dye is sepaated byfiltration and is suspended in water slightly alk-' llinized with sodiumcarbonate. It is then filtered and lried.

The monoazodye thus obtained has the following fornula:

The dye is a black-brown powder, which is very suit- ;ble for dyeingwool by the known metachrorne process, hus giving a dark-brown shadewith very good wet and ight fastness.

The dyeing can also be carried out by employing suc- :essive chromation.

Example 2 22.5 parts of 1-hydroxy-2-amino-4-nitro-6-propionyltIIliIlObenzene are diazotized by following the procedure )f Example 1. Thesuspension of d-iazocompound is neuralized with Na CO and is introducedat 0 C. into a olution of 14.9 parts ofZ-hydroxy-S,6,7,'8-tetrahydroiaphtha'lene in 40 parts of water, 4 partsof NaOH and 50 parts by volume of pyridine.

The coupling occurs very quickly. The dye product )btained aftercoupling contains about 30% by volume of Jyri-dine.

The dye, which is isolated and dried, is a brown powder raving thefollowing formula:

CIIH OH CHaGHzOONH- N=N [his dye possesses shade and properties similarto the dye )f Example 1.

Example 3 20 parts of 1hydroxy-Z-amino-4-chloro-6-acetaminoaenzene arediazotized and coupled as in Example 1.

A monoazo dye having the following formula:

(Ina 9H obtained in the form of a dark-brown powder which inges woolusing the rnetaclrrome process. A brown :hade, clearer than that of thepreceding example, having t violet tint and good wet and light fastness,is obtained.

A p This dye is also suitable for dyeing followed by successivechromation.

Examples 4-7 These examples are conducted by following the procedure ofExample 1. In each case, 2-hydroxy-5,6,7,8-tetraihydnonap'hthalene isused as the coupling component. The various other dye componentsemployed and the results obtained are reported in Table I, shown below.

TAB LE I Diazotized base coupled Color shade after chromation Ex. No.with 2-hydroxy-4, 5, 6, 7- and characteristics withretetrahydronaphthalene spect to the dye of Ex. 1.

4 1-hydroxy-2-amino-Lnitro- Substantially the same shade Mormylarninobenzene. of brown; slightly lower light fastness.

5 1-hydroxy-2amino-4-nitro- Brown with a violet tint.

fi-chloroacetamino benzene.

6 l-hydroxy-Zamino--nitro- Almost equal shade; slightly6-methoxyearbonylaminolower light fastness. benzene.

7 1-hydroxy-2-amin0-4-eh1oro- Brown with a violet tint;

6-propionylamin0benzene. better tastness to fulling.

Many variations and modifications can, of course, be

' made without departing from the spirit and scope of the presentinvention.

Having thus described the present invention, what it is desired tosecure and claim by Letters Patent is:

1. A monoazo dye having the formula (j... p X a wherein X is selectedfrom the group consisting of chlorine, and a N0 group, and Y is selectedfrom the group consisting of a caoboxylamino radical containing from 1to 4 carbon atoms, a canbo-xylarnino radical containing from 1 to 4carbon atoms and further containing chlorine in the hydnocanbon chain,and an alkoxy-carboxylamino radical containing from 1 to 4 carbonatoms.-

2. The monoazo dye of claim 1 wherein X is a chlorine atom.

3. The monoazo dye of claim 1 wherein X is a N0 group.

4. The monoazo dye of claim 1 wherein Y is a carboxylamino radicalcontaining from 1 to 4 canbon atoms.

5. The monoazo dye of claim 1 wherein Y is a canboxylamino radicalcontaining from 1 to 4 carbon atoms and further containing chlorine inthe hydrocanbon chain.

6. The monoazo dye of claim 1 wherein Y is an :alkoxy-oarboxylaminoradical containing from 1 to 4 carbon atoms.

7. The monoazo dye which has the formula:

8. The monoazo dye which has the iormula:

OIH OH NO: H

9. The monoazo dye which has the formula:

10. The monoazo dye which has the formula:

OH OH H 0 0 NH@NN@ 1 N O 2 H 11. The monoazo dye which has the formula:

13. The monoazo dye which has the formula:

OH OH References Cited by the Examiner UNITED STATES PATENTS 4/ 1953Steinemann 260-151 X 10/1956 Buehler 260151 X FOREIGN PATENTS 2/ 1936Germany. 5/ 1957 Germany. 3/ 1960 Germany.

OTHER REFERENCES Colour Index, 2nd Edition (1956), V01. 3, TP 910 S6,

Conzetti:

German application, Serial No. G 13,644,

printed January 19, 1956 ('Kl.22a 2).

CHARLES B. PARKER, Primary Examiner. 40 N. S. MILESTONE, R. I. FINNEGAN,F. D. HIGEL,

Assistant Examiners,

1. A MONOAZO DYE HAVING THE FORMULA